Copper lanthanum titanate La2/3Cu3Ti4−xFexO12−δ x = 0–1 was doped with Fe3+ cations. The diagram of the dependence of the tolerance factor on the relative electronegativity of cations for all studied compositions was represented. It was shown that all the compositions exist in the region of existence of distorted perovskite. X-ray diffraction and X-ray phase analysis methods established the region of existence of solid solutions of La2/3Cu3Ti4−xFexO12−δ obtained by ceramic technology, which was 0 ⩽ x ⩽ 0.4.